CA2972107A1 - Preparation of n,n-(di)alkylaminoalkyl(meth)acrylamide or n,n-(di)alkylaminoalkyl(meth)acrylate and the quaternary ammonium salts thereof as flocculating aids and gelling agents - Google Patents
Preparation of n,n-(di)alkylaminoalkyl(meth)acrylamide or n,n-(di)alkylaminoalkyl(meth)acrylate and the quaternary ammonium salts thereof as flocculating aids and gelling agents Download PDFInfo
- Publication number
- CA2972107A1 CA2972107A1 CA2972107A CA2972107A CA2972107A1 CA 2972107 A1 CA2972107 A1 CA 2972107A1 CA 2972107 A CA2972107 A CA 2972107A CA 2972107 A CA2972107 A CA 2972107A CA 2972107 A1 CA2972107 A1 CA 2972107A1
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- Prior art keywords
- meth
- alkylaminoalkyl
- acrylamide
- acrylate
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000000278 alkyl amino alkyl group Chemical group 0.000 title claims abstract description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 60
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000003349 gelling agent Substances 0.000 title claims description 6
- 230000003311 flocculating effect Effects 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 72
- -1 cyclic alkyl radical Chemical class 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000007717 exclusion Effects 0.000 claims description 4
- 239000000834 fixative Substances 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- 238000012674 dispersion polymerization Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- CMQPKQNBMBISIV-UHFFFAOYSA-N methyl 3-(3-methoxy-2-methyl-3-oxopropyl)sulfanyl-2-methylpropanoate Chemical compound COC(=O)C(C)CSCC(C)C(=O)OC CMQPKQNBMBISIV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 description 53
- 239000000376 reactant Substances 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- GROXSGRIVDMIEN-UHFFFAOYSA-N 2-methyl-n-prop-2-enylprop-2-enamide Chemical compound CC(=C)C(=O)NCC=C GROXSGRIVDMIEN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 150000003926 acrylamides Chemical class 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 5
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011552 falling film Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical class CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000007098 aminolysis reaction Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229920013750 conditioning polymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 2
- ZUXUNWLVIWKEHB-UHFFFAOYSA-N n',n'-dimethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN ZUXUNWLVIWKEHB-UHFFFAOYSA-N 0.000 description 2
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- HRHKBQXBOFVHMK-UHFFFAOYSA-N 2-(2,2-dimethylpropyl)-1,1-dimethylhydrazine Chemical compound CN(C)NCC(C)(C)C HRHKBQXBOFVHMK-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 1
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OWRQMOQBTYIJQC-UHFFFAOYSA-N n',n'-di(propan-2-yl)butane-1,4-diamine Chemical compound CC(C)N(C(C)C)CCCCN OWRQMOQBTYIJQC-UHFFFAOYSA-N 0.000 description 1
- CURJNMSGPBXOGK-UHFFFAOYSA-N n',n'-di(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN CURJNMSGPBXOGK-UHFFFAOYSA-N 0.000 description 1
- QPGRDTXELAFGRG-UHFFFAOYSA-N n',n'-di(propan-2-yl)propane-1,3-diamine Chemical compound CC(C)N(C(C)C)CCCN QPGRDTXELAFGRG-UHFFFAOYSA-N 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- JILXUIANNUALRZ-UHFFFAOYSA-N n',n'-diethylbutane-1,4-diamine Chemical compound CCN(CC)CCCCN JILXUIANNUALRZ-UHFFFAOYSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- TZBFEBDATQDIHX-UHFFFAOYSA-N n',n'-diethylhexane-1,6-diamine Chemical compound CCN(CC)CCCCCCN TZBFEBDATQDIHX-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 description 1
- GLDVKMPSACNWFV-UHFFFAOYSA-N n',n'-dipropylbutane-1,4-diamine Chemical compound CCCN(CCC)CCCCN GLDVKMPSACNWFV-UHFFFAOYSA-N 0.000 description 1
- DMDXQHYISPCTGF-UHFFFAOYSA-N n',n'-dipropylethane-1,2-diamine Chemical compound CCCN(CCC)CCN DMDXQHYISPCTGF-UHFFFAOYSA-N 0.000 description 1
- GZUCMODGDIGMBI-UHFFFAOYSA-N n',n'-dipropylpropane-1,3-diamine Chemical compound CCCN(CCC)CCCN GZUCMODGDIGMBI-UHFFFAOYSA-N 0.000 description 1
- MXJYVLYENVWKQX-UHFFFAOYSA-N n'-ethyl-n-methylethane-1,2-diamine Chemical compound CCNCCNC MXJYVLYENVWKQX-UHFFFAOYSA-N 0.000 description 1
- PVFDVUMXTHUUNU-UHFFFAOYSA-N n'-ethyl-n-methylpropane-1,3-diamine Chemical compound CCNCCCNC PVFDVUMXTHUUNU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CHKWHTPECBLEBR-UHFFFAOYSA-N n-methyl-n'-propylethane-1,2-diamine Chemical compound CCCNCCNC CHKWHTPECBLEBR-UHFFFAOYSA-N 0.000 description 1
- LAODUQWLGGBAKR-UHFFFAOYSA-N n-methyl-n'-propylpropane-1,3-diamine Chemical compound CCCNCCCNC LAODUQWLGGBAKR-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention describes a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof with a low content of the compounds corresponding to the formula (IV).
Description
Preparation of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof as flocculating aids and gelling agents The present invention describes a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof with a low content of the compounds corresponding to the formula (IV).
The preparation of dimethylaminopropylmethacrylamide (DMAPMA) is known from the prior art.
EP 0 960 877 (Elf Atochem S.A.) describes a continuous process for preparing methacrylate esters of dialkylamino alcohols. Dialkylamino alcohols are reacted with generally methyl (meth)acrylate, and the dialkylaminoalkyl (meth)acrylate is obtained by the following method:
The mixture of the starting materials (methyl (meth)acrylate and dialkylamino alcohol) is supplied continuously to a stirred reactor together with a tetraalkyl titanate as catalyst (for example tetrabutyl, tetraethyl or tetra(2-ethylhexyl) titanate) and at least one polymerization inhibitor (for example phenothiazine, tert-butylcatechol, hydroquinone monomethyl ether or hydroquinone), where the conversion to the dialkylamino (meth)acrylate is effected at a temperature of 90 C-120 C
with simultaneous continuous removal of the azeotropic methyl (meth)acrylate/methanol mixture.
The crude reaction mixture (crude ester) is fed to a first distillation column, wherein an essentially catalyst-free stream is drawn off at the top of the distillation column under reduced pressure and the catalyst and a little dialkylaminoalkyl (meth)acrylate are drawn off at the bottom of the distillation column. The top stream from the first distillation column is then fed to a second distillation column in which, under reduced pressure, a stream of low-boiling products comprising a little dialkylaminoalkyl (meth)acrylate is drawn off at the top and a stream consisting of mainly dialkylaminoalkyl (meth)acrylate and polymerization inhibitor(s) is drawn off at the bottom and is supplied to a third distillation column. In the third distillation column, under reduced pressure, a rectification is conducted, in which the desired pure dialkylaminoalkyl (meth)acrylate is drawn off at the top and essentially the polymerization inhibitor(s) at the bottom. After further purification with the aid of a film evaporator, the bottom stream from the first distillation column is recycled into the reactor, just like the top stream from the second distillation column.
This process dispenses with dewatering of the alcohols before use, which can lead to increased deactivation of the tetraalkyl titanate used owing to hydrolysis that extends as far as formation of unwanted solid deposits. Furthermore, the process has the disadvantage that the catalyst is subjected to thermal stress at relatively high temperatures in the bottom of the first distillation column. This can easily lead to breakdown of the catalyst.
In this process, there are a total of two overhead rectifications both of the unconverted reactants and of the product. This entails very high energy costs and a total of 4 rectification columns, some
The preparation of dimethylaminopropylmethacrylamide (DMAPMA) is known from the prior art.
EP 0 960 877 (Elf Atochem S.A.) describes a continuous process for preparing methacrylate esters of dialkylamino alcohols. Dialkylamino alcohols are reacted with generally methyl (meth)acrylate, and the dialkylaminoalkyl (meth)acrylate is obtained by the following method:
The mixture of the starting materials (methyl (meth)acrylate and dialkylamino alcohol) is supplied continuously to a stirred reactor together with a tetraalkyl titanate as catalyst (for example tetrabutyl, tetraethyl or tetra(2-ethylhexyl) titanate) and at least one polymerization inhibitor (for example phenothiazine, tert-butylcatechol, hydroquinone monomethyl ether or hydroquinone), where the conversion to the dialkylamino (meth)acrylate is effected at a temperature of 90 C-120 C
with simultaneous continuous removal of the azeotropic methyl (meth)acrylate/methanol mixture.
The crude reaction mixture (crude ester) is fed to a first distillation column, wherein an essentially catalyst-free stream is drawn off at the top of the distillation column under reduced pressure and the catalyst and a little dialkylaminoalkyl (meth)acrylate are drawn off at the bottom of the distillation column. The top stream from the first distillation column is then fed to a second distillation column in which, under reduced pressure, a stream of low-boiling products comprising a little dialkylaminoalkyl (meth)acrylate is drawn off at the top and a stream consisting of mainly dialkylaminoalkyl (meth)acrylate and polymerization inhibitor(s) is drawn off at the bottom and is supplied to a third distillation column. In the third distillation column, under reduced pressure, a rectification is conducted, in which the desired pure dialkylaminoalkyl (meth)acrylate is drawn off at the top and essentially the polymerization inhibitor(s) at the bottom. After further purification with the aid of a film evaporator, the bottom stream from the first distillation column is recycled into the reactor, just like the top stream from the second distillation column.
This process dispenses with dewatering of the alcohols before use, which can lead to increased deactivation of the tetraalkyl titanate used owing to hydrolysis that extends as far as formation of unwanted solid deposits. Furthermore, the process has the disadvantage that the catalyst is subjected to thermal stress at relatively high temperatures in the bottom of the first distillation column. This can easily lead to breakdown of the catalyst.
In this process, there are a total of two overhead rectifications both of the unconverted reactants and of the product. This entails very high energy costs and a total of 4 rectification columns, some
2 of which have to have very large dimensions. The process is therefore afflicted with very high capital and operating costs.
EP 0 968 995 (Mitsubishi Gas Chemical Comp.) describes a continuous process for preparing alkyl (meth)acrylates using a reaction column. The transesterification reaction is effected here directly in a distillation column (i.e. reactor and distillation column for removal of methyl (meth)acrylate/methanol azeotrope form one apparatus), which is supplied continuously with the starting materials (methyl (meth)acrylate and alcohol). The necessary catalyst, here likewise preferably a titanium compound, is present in the distillation column. In the case of a homogeneous catalyst, the catalyst is metered continuously into the distillation column.
However, the use of homogeneous catalysts in a distillation column, because of the flushing effect resulting from the liquid reflux in the distillation column, leads to elevated catalyst demand and, in the event of occurrence of solid catalyst precipitation, to soiling of the column internals. In the case of a heterogeneous catalyst, the catalyst is in the reaction column. However, the positioning of the catalyst in the distillation column is disadvantageous because an elevated pressure drop then occurs in the distillation column and, in addition, a very high level of cost and inconvenience is necessary for the regular cleaning of the distillation column. Moreover, heterogeneous catalysts can become deactivated, for example as a result of unwanted polymerization.
US 8,674,133 (Evonik Rohm GmbH) describes a continuous process for preparing alkylamino(meth)acrylamides by means of continuous aminolysis. The reduction in the crosslinker content is achieved here via complex processing steps, especially distillations.
The above-described processes lead to the formation of various by-products, most of which cannot remain in the end product. The removal of the by-products leads to the known disadvantages, for example yield losses and elevated capital, operating and maintenance costs as a result of the purification steps required.
In the synthesis of N,N-(di)alkylaminopropylmethacrylamides and the quaternary ammonium salts thereof, the formation of compounds of the formula (IV) Ro 0 X_Re (Iv) is particularly undesirable. An elevated proportion of this compound in the end product leads to premature and uncontrolled crosslinking in the polymerization.
The problem addressed was that of providing a process with which N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof can be prepared with a low content of compounds of the formula (IV). Another problem addressed was that of providing a process for preparing monomers which enables the preparation of soluble or non-coagulating polymers.
EP 0 968 995 (Mitsubishi Gas Chemical Comp.) describes a continuous process for preparing alkyl (meth)acrylates using a reaction column. The transesterification reaction is effected here directly in a distillation column (i.e. reactor and distillation column for removal of methyl (meth)acrylate/methanol azeotrope form one apparatus), which is supplied continuously with the starting materials (methyl (meth)acrylate and alcohol). The necessary catalyst, here likewise preferably a titanium compound, is present in the distillation column. In the case of a homogeneous catalyst, the catalyst is metered continuously into the distillation column.
However, the use of homogeneous catalysts in a distillation column, because of the flushing effect resulting from the liquid reflux in the distillation column, leads to elevated catalyst demand and, in the event of occurrence of solid catalyst precipitation, to soiling of the column internals. In the case of a heterogeneous catalyst, the catalyst is in the reaction column. However, the positioning of the catalyst in the distillation column is disadvantageous because an elevated pressure drop then occurs in the distillation column and, in addition, a very high level of cost and inconvenience is necessary for the regular cleaning of the distillation column. Moreover, heterogeneous catalysts can become deactivated, for example as a result of unwanted polymerization.
US 8,674,133 (Evonik Rohm GmbH) describes a continuous process for preparing alkylamino(meth)acrylamides by means of continuous aminolysis. The reduction in the crosslinker content is achieved here via complex processing steps, especially distillations.
The above-described processes lead to the formation of various by-products, most of which cannot remain in the end product. The removal of the by-products leads to the known disadvantages, for example yield losses and elevated capital, operating and maintenance costs as a result of the purification steps required.
In the synthesis of N,N-(di)alkylaminopropylmethacrylamides and the quaternary ammonium salts thereof, the formation of compounds of the formula (IV) Ro 0 X_Re (Iv) is particularly undesirable. An elevated proportion of this compound in the end product leads to premature and uncontrolled crosslinking in the polymerization.
The problem addressed was that of providing a process with which N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof can be prepared with a low content of compounds of the formula (IV). Another problem addressed was that of providing a process for preparing monomers which enables the preparation of soluble or non-coagulating polymers.
3 The problem was solved by a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate of the general formula (I) X¨R2¨N/R3 \R4 (I) where R is hydrogen or methyl X is NH or 0 R2, R3, R4 are each a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, having a content of less than 1200 ppm of the compound (IV) of the general formula Ro 0 (Iv) where R5 in each case is a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, characterized in that the oxygen concentration is < 1000 ppm in the liquid phase in at least one component step of the preparation.
The problem was solved by a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate of the general formula (I) and the quaternary ammonium salts thereof having a content of compounds of the formula (IV) of less than 1200 ppm, characterized in that operation is effected with a reduced oxygen content.
The content of the compounds of formula (IV) is preferably less than 1000 ppm, more preferably less than 850 ppm, most preferably less than 700 ppm.
The problem was solved by a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate of the general formula (I) and the quaternary ammonium salts thereof having a content of compounds of the formula (IV) of less than 1200 ppm, characterized in that operation is effected with a reduced oxygen content.
The content of the compounds of formula (IV) is preferably less than 1000 ppm, more preferably less than 850 ppm, most preferably less than 700 ppm.
4 The notation "(meth)acrylate" here means both methacrylate, for example methyl methacrylate, ethyl methacrylate, etc., and acrylate, for example methyl acrylate, ethyl acrylate, etc., and mixtures of the two.
The problem was also solved by a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1 having a content of less than 1200 ppm of the compound of the formula (IV) or quaternary ammonium salts thereof which are used for preparation of soluble or non-coagulating polymers.
Soluble or non-coagulating polymers in this context means that the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates prepared in accordance with the invention, after polymerization or copolymerization with other compounds, can be brought into solution in a suitable solvent or form a non-coagulating emulsion or dispersion. It is likewise possible for the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates quaternized in accordance with the invention, after polymerization or copolymerization, to be brought into solution in suitable solvents.
It has been found that, surprisingly, the formation of compounds of the formula (IV) can be minimized by the reduction of the oxygen level in the reaction system.
The reduction of the oxygen level means that, in the preparation of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate, the oxygen concentration is < 1000 ppm in the liquid phase in at least one component step. Preferably, the oxygen concentration is less than 1000 ppm in the liquid phase in the conversion of the reactants in the reaction vessel or the stirred tank cascade.
Ideally, the reaction is conducted with exclusion of oxygen. The reaction can be conducted either under vacuum or under a protective gas atmosphere, for example under an N2 or argon atmosphere.
It has been found that the reduction in the residence time can also contribute to the reduction of the formation of compounds of the formula (IV). A reduction in the residence time without a considerable reduction in the space-time yield can be achieved via the following measures:
- use of more active catalysts, - use of elevated amounts of catalyst, - a shift in equilibrium as a result of increased alcohol removal, for example by virtue of higher column capacities and/or more energy input.
It has been found that, surprisingly, the reduction in the reaction temperature also leads to a reduction in the content of compounds of formula (IV). In order to avoid the high temperatures that are customary in the process at the end of the reaction, the pressure is reduced at the same time.
The problem was also solved by a process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1 having a content of less than 1200 ppm of the compound of the formula (IV) or quaternary ammonium salts thereof which are used for preparation of soluble or non-coagulating polymers.
Soluble or non-coagulating polymers in this context means that the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates prepared in accordance with the invention, after polymerization or copolymerization with other compounds, can be brought into solution in a suitable solvent or form a non-coagulating emulsion or dispersion. It is likewise possible for the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates quaternized in accordance with the invention, after polymerization or copolymerization, to be brought into solution in suitable solvents.
It has been found that, surprisingly, the formation of compounds of the formula (IV) can be minimized by the reduction of the oxygen level in the reaction system.
The reduction of the oxygen level means that, in the preparation of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate, the oxygen concentration is < 1000 ppm in the liquid phase in at least one component step. Preferably, the oxygen concentration is less than 1000 ppm in the liquid phase in the conversion of the reactants in the reaction vessel or the stirred tank cascade.
Ideally, the reaction is conducted with exclusion of oxygen. The reaction can be conducted either under vacuum or under a protective gas atmosphere, for example under an N2 or argon atmosphere.
It has been found that the reduction in the residence time can also contribute to the reduction of the formation of compounds of the formula (IV). A reduction in the residence time without a considerable reduction in the space-time yield can be achieved via the following measures:
- use of more active catalysts, - use of elevated amounts of catalyst, - a shift in equilibrium as a result of increased alcohol removal, for example by virtue of higher column capacities and/or more energy input.
It has been found that, surprisingly, the reduction in the reaction temperature also leads to a reduction in the content of compounds of formula (IV). In order to avoid the high temperatures that are customary in the process at the end of the reaction, the pressure is reduced at the same time.
5 The reduction in the pressure in the reaction is preferably effected toward the end of the reaction.
Accordingly, the pressure at the start of the reaction can also be increased.
The process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylate comprises the aminolysis or alcoholysis of alkyl (meth)acrylates with amines or alcohols with release of alcohols.
The (meth)acrylate feed reactant is supplied continuously to a suitable reaction apparatus, it being possible to use either an individual reaction vessel or a cascade of two or more reaction vessels connected in series. Such a cascade may consist, for example, of 2, 3, 4, 5, 6 or optionally several individual reaction vessels. In a preferred embodiment, a cascade of 3 continuously operated stirred tanks arranged in series is used.
The (meth)acrylate feed reactant can be effected in various ways. It is possible, for example, to feed a reactant stream only to the first reaction vessel of the cascade or else to divide the reactant stream into substreams and to supply these substreams to all or just some of the series-connected reaction vessels of the cascade. It is likewise possible to undertake the feeding of the reactant stream via the low boiler discharge distillation column and/or the reaction apparatuses. It may be advantageous to feed the reactant stream only into the low boiler discharge distillation column or, in a further embodiment, to divide the reactant stream into substreams which are then supplied either to the low boiler discharge distillation column or to the first or optionally two or more reaction vessels of the cascade.
Suitable alkyl (meth)acrylates are compounds of the formula (II) Ro 0 0¨Ri (II) where Ro is hydrogen or methyl R1 is linear or branched alkyl radical having 1 to 10, preferably 1 to 4, carbon atoms.
Typical examples of these are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 3-methylbutyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, ethylhexyl (meth)acrylate or decyl (meth)acrylate.
It is advisable that all reaction vessels have a vapour draw to the distillation column for removal of the alcohol released in the reaction.
Accordingly, the pressure at the start of the reaction can also be increased.
The process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylate comprises the aminolysis or alcoholysis of alkyl (meth)acrylates with amines or alcohols with release of alcohols.
The (meth)acrylate feed reactant is supplied continuously to a suitable reaction apparatus, it being possible to use either an individual reaction vessel or a cascade of two or more reaction vessels connected in series. Such a cascade may consist, for example, of 2, 3, 4, 5, 6 or optionally several individual reaction vessels. In a preferred embodiment, a cascade of 3 continuously operated stirred tanks arranged in series is used.
The (meth)acrylate feed reactant can be effected in various ways. It is possible, for example, to feed a reactant stream only to the first reaction vessel of the cascade or else to divide the reactant stream into substreams and to supply these substreams to all or just some of the series-connected reaction vessels of the cascade. It is likewise possible to undertake the feeding of the reactant stream via the low boiler discharge distillation column and/or the reaction apparatuses. It may be advantageous to feed the reactant stream only into the low boiler discharge distillation column or, in a further embodiment, to divide the reactant stream into substreams which are then supplied either to the low boiler discharge distillation column or to the first or optionally two or more reaction vessels of the cascade.
Suitable alkyl (meth)acrylates are compounds of the formula (II) Ro 0 0¨Ri (II) where Ro is hydrogen or methyl R1 is linear or branched alkyl radical having 1 to 10, preferably 1 to 4, carbon atoms.
Typical examples of these are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 3-methylbutyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, ethylhexyl (meth)acrylate or decyl (meth)acrylate.
It is advisable that all reaction vessels have a vapour draw to the distillation column for removal of the alcohol released in the reaction.
6 In particular embodiments, it has been found to be advantageous to introduce the discharge from one tank of the cascade into the bottom of the next tank of the cascade downstream in each case.
The reactant is supplied continuously to the low boiler discharge distillation column for dewatering.
Suitable reactants are compounds of the formula (III) X¨R2¨N
\ R4 (III) with X = OH or NH2 R2, R3, R4 each a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl.
Examples of useful reactants include the following compounds:
dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, diisopropylaminoethylamine, dibutylaminoethylamine, disobutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, diisopropylaminopropylamine, dibutylaminopropylamine, disobutylaminopropylamine, dimethylaminobutylamine, diethylaminobutylamine, dipropylaminobutylamine, diisopropylaminobutylamine, dibutylaminobutylamine, disobutylaminobutylamine, dimethylaminohexylamine, diethylaminohexylamine, dimethylaminoneopentylamine, methylethylaminopropylamine, methylpropylaminopropylamine, methylpropylaminoethylamine, methylethylaminoethylamine, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, dipropylaminoethyl alcohol, diisopropylaminoethyl alcohol, dibutylaminoethyl alcohol, disobutylaminoethyl alcohol, dimethylaminopropyl alcohol, diethylaminopropyl alcohol, dipropylaminopropyl alcohol, diisopropylaminopropyl alcohol, dibutylaminopropyl alcohol, disobutylaminopropyl alcohol, dimethylaminobutyl alcohol, diethylaminobutyl alcohol, dipropylaminobutyl alcohol, diisopropylaminobutyl alcohol, dibutylaminobutyl alcohol, disobutylaminobutyl alcohol, dimethylaminohexyl alcohol, diethylaminohexyl alcohol, dimethylaminoneopentyl alcohol, methylethylaminopropyl alcohol, methylpropylaminopropyl alcohol, methylpropylaminoethyl alcohol, methylethylaminoethyl alcohol.
Particular preference is given to dimethylaminopropylamine, dimethylaminoethylamine, dimethylaminohexylamine, dimethylaminopropyl alcohol, dimethylaminoethyl alcohol, and dimethylaminohexyl alcohol.
The reactant is supplied continuously to the low boiler discharge distillation column for dewatering.
Suitable reactants are compounds of the formula (III) X¨R2¨N
\ R4 (III) with X = OH or NH2 R2, R3, R4 each a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl.
Examples of useful reactants include the following compounds:
dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, diisopropylaminoethylamine, dibutylaminoethylamine, disobutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, diisopropylaminopropylamine, dibutylaminopropylamine, disobutylaminopropylamine, dimethylaminobutylamine, diethylaminobutylamine, dipropylaminobutylamine, diisopropylaminobutylamine, dibutylaminobutylamine, disobutylaminobutylamine, dimethylaminohexylamine, diethylaminohexylamine, dimethylaminoneopentylamine, methylethylaminopropylamine, methylpropylaminopropylamine, methylpropylaminoethylamine, methylethylaminoethylamine, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, dipropylaminoethyl alcohol, diisopropylaminoethyl alcohol, dibutylaminoethyl alcohol, disobutylaminoethyl alcohol, dimethylaminopropyl alcohol, diethylaminopropyl alcohol, dipropylaminopropyl alcohol, diisopropylaminopropyl alcohol, dibutylaminopropyl alcohol, disobutylaminopropyl alcohol, dimethylaminobutyl alcohol, diethylaminobutyl alcohol, dipropylaminobutyl alcohol, diisopropylaminobutyl alcohol, dibutylaminobutyl alcohol, disobutylaminobutyl alcohol, dimethylaminohexyl alcohol, diethylaminohexyl alcohol, dimethylaminoneopentyl alcohol, methylethylaminopropyl alcohol, methylpropylaminopropyl alcohol, methylpropylaminoethyl alcohol, methylethylaminoethyl alcohol.
Particular preference is given to dimethylaminopropylamine, dimethylaminoethylamine, dimethylaminohexylamine, dimethylaminopropyl alcohol, dimethylaminoethyl alcohol, and dimethylaminohexyl alcohol.
7 Catalysts and polymerization inhibitors are likewise preferably metered continuously into the reaction apparatus.
Transesterification catalysts used may be any catalysts known from the prior art.
Useful catalysts include, for example, zirconium acetylacetonate and further 1,3-diketones of zirconium; in addition, it is possible to use mixtures of alkali metal cyanates or alkali metal thiocyanates and alkali metal halides, and also tin compounds, for example dioctyltin oxide, alkaline earth metal oxides or alkaline earth metal hydroxides, for example LOH, CaO, Ca(OH)2, MgO, Mg(OH)2, or mixtures of the aforementioned compounds, and also alkali metal hydroxides, alkali metal alkoxides and lithium chloride and lithium hydroxide; it is also possible to use mixtures of the aforementioned compounds with the aforementioned alkaline earth metal compounds and lithium salts, especially lithium chloride and calcium hydroxide, dialkyltin oxides, for example dioctyltin oxide, alkali metal carbonates, alkali metal carbonates together with quaternary ammonium salts, for example tetrabutylammonium hydroxide or hexadecyltrimethylammonium bromide, and also mixed catalysts composed of diorganyltin oxide and organyltin halide, acidic ion exchangers, phosphorus-molybdenum heteropolyacids, titanium alkoxides, for example isopropyl titanate, chelate compounds of the metals titanium, zirconium, iron or zinc with 1,3-dicarbonyl compounds, lead compounds, for example lead oxides, lead hydroxides, lead alkoxides, lead carbonates or lead salts of carboxylic acids, and alkaline earth metal amides, especially lithium amide. Likewise suitable are alkali metal alkoxides, preferably lithium alkoxides, especially lithium methoxide. Particular preference is given to a catalyst mixture composed of dialkyltin oxide and alkyl titanate, for example dioctyltin oxide and isopropyl titanate, in a ratio of about 1:3 (Y by weight) to 3:1 (/0 by weight). The catalyst mixture is used in amounts of 0.1%-10% by weight, based on the amount of the reactants used.
Pre-activation of the catalyst has been found to be advantageous. This involves mixing or dispersing the catalysts, heating them to temperatures of 90 C to 120 C and stirring them for 2 to 3 h until a homogeneous clear solution has formed.
Examples of useful polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether and the piperidyl derivatives.
The reduction in the oxygen level may require that the stabilizers requiring oxygen that are typically used be replaced by stabilizers that work in an oxygen-free manner.
Preference is given to polymerization inhibitors selected from the group of bis(2-methoxycarbonylpropyl) sulphide, N,N-diethylhydroxylamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl or N,IV-diphenyl-p-phenylenediamine and derivatives thereof (for example esters, amides etc.).
The choice of the starting materials is particularly advantageously made such that it is possible to shift the equilibrium to the side of the products with the removal of the alcohol from the reaction
Transesterification catalysts used may be any catalysts known from the prior art.
Useful catalysts include, for example, zirconium acetylacetonate and further 1,3-diketones of zirconium; in addition, it is possible to use mixtures of alkali metal cyanates or alkali metal thiocyanates and alkali metal halides, and also tin compounds, for example dioctyltin oxide, alkaline earth metal oxides or alkaline earth metal hydroxides, for example LOH, CaO, Ca(OH)2, MgO, Mg(OH)2, or mixtures of the aforementioned compounds, and also alkali metal hydroxides, alkali metal alkoxides and lithium chloride and lithium hydroxide; it is also possible to use mixtures of the aforementioned compounds with the aforementioned alkaline earth metal compounds and lithium salts, especially lithium chloride and calcium hydroxide, dialkyltin oxides, for example dioctyltin oxide, alkali metal carbonates, alkali metal carbonates together with quaternary ammonium salts, for example tetrabutylammonium hydroxide or hexadecyltrimethylammonium bromide, and also mixed catalysts composed of diorganyltin oxide and organyltin halide, acidic ion exchangers, phosphorus-molybdenum heteropolyacids, titanium alkoxides, for example isopropyl titanate, chelate compounds of the metals titanium, zirconium, iron or zinc with 1,3-dicarbonyl compounds, lead compounds, for example lead oxides, lead hydroxides, lead alkoxides, lead carbonates or lead salts of carboxylic acids, and alkaline earth metal amides, especially lithium amide. Likewise suitable are alkali metal alkoxides, preferably lithium alkoxides, especially lithium methoxide. Particular preference is given to a catalyst mixture composed of dialkyltin oxide and alkyl titanate, for example dioctyltin oxide and isopropyl titanate, in a ratio of about 1:3 (Y by weight) to 3:1 (/0 by weight). The catalyst mixture is used in amounts of 0.1%-10% by weight, based on the amount of the reactants used.
Pre-activation of the catalyst has been found to be advantageous. This involves mixing or dispersing the catalysts, heating them to temperatures of 90 C to 120 C and stirring them for 2 to 3 h until a homogeneous clear solution has formed.
Examples of useful polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether and the piperidyl derivatives.
The reduction in the oxygen level may require that the stabilizers requiring oxygen that are typically used be replaced by stabilizers that work in an oxygen-free manner.
Preference is given to polymerization inhibitors selected from the group of bis(2-methoxycarbonylpropyl) sulphide, N,N-diethylhydroxylamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl or N,IV-diphenyl-p-phenylenediamine and derivatives thereof (for example esters, amides etc.).
The choice of the starting materials is particularly advantageously made such that it is possible to shift the equilibrium to the side of the products with the removal of the alcohol from the reaction
8 mixture. The removal of the alcohol can be effected by distillation by virtue of its lower boiling point compared to the reactant used and/or through the formation of an azeotrope.
The reactant used may contain water. The amount of water in the reactant used is below 5000 ppm. Before it enters the reaction apparatus, the reactant is dewatered by distillation, preferably by means of a distillation column. This involves drawing off the water present in the reactant overhead. For avoidance of contamination of the low boiler output with the reactant used, the reactant is preferably applied in the lower portion of the distillation column. The reactant used can also be dewatered in other ways:
- by means of an upstream dewatering distillation column or - by treatment with a dehydrating agent, for example a molecular sieve, or - by a membrane separation method, for example a pervaporation.
The reason why the dewatering is important is because the water present in the reactant can lead to irreversible damage to the catalyst in the reactor. The water present in the reactant leads to the formation of by-products and should therefore be strictly avoided. This dewatering step avoids the hydrolysis of the catalyst and the associated costs resulting from elevated catalyst use amounts and resulting from problems with solid precipitates. Moreover, the purity of the product is increased by a reduced proportion of by-products.
The reaction is effected in the reaction apparatus at a temperature in the range between 70 C and 160 C, according to the system and operating pressure.
According to the invention, the reaction temperature can be reduced in order to minimize the formation of compounds of the formula (IV). Preference is given to reducing the temperature to 80-120 C, more preferably to temperatures between 80 C and 90 C. In order to achieve maximum completeness of conversion, reduced pressure is therefore employed. In a continuous mode of operation, the conversion is preferably effected in a tank cascade. All cascade stages can work under reduced pressure; preferably, the pressure is reduced in the last stage of the cascade.
Preference is given to working under a vacuum between 900 and 0 bar.
According to the invention, the decrease in the residence time can also lead to a reduction in the content of compounds of formula (IV) in the end product.
Residence times between 0.1 and 11 h, preferably between 1 and 5 h, lead to a noticeable reduction in the content of compounds of formula (IV) in the end product.
For a sufficiently high conversion in spite of a reduced residence time, it is necessary that more active catalysts be used or/and that the amount of catalyst be increased.
The reactant used may contain water. The amount of water in the reactant used is below 5000 ppm. Before it enters the reaction apparatus, the reactant is dewatered by distillation, preferably by means of a distillation column. This involves drawing off the water present in the reactant overhead. For avoidance of contamination of the low boiler output with the reactant used, the reactant is preferably applied in the lower portion of the distillation column. The reactant used can also be dewatered in other ways:
- by means of an upstream dewatering distillation column or - by treatment with a dehydrating agent, for example a molecular sieve, or - by a membrane separation method, for example a pervaporation.
The reason why the dewatering is important is because the water present in the reactant can lead to irreversible damage to the catalyst in the reactor. The water present in the reactant leads to the formation of by-products and should therefore be strictly avoided. This dewatering step avoids the hydrolysis of the catalyst and the associated costs resulting from elevated catalyst use amounts and resulting from problems with solid precipitates. Moreover, the purity of the product is increased by a reduced proportion of by-products.
The reaction is effected in the reaction apparatus at a temperature in the range between 70 C and 160 C, according to the system and operating pressure.
According to the invention, the reaction temperature can be reduced in order to minimize the formation of compounds of the formula (IV). Preference is given to reducing the temperature to 80-120 C, more preferably to temperatures between 80 C and 90 C. In order to achieve maximum completeness of conversion, reduced pressure is therefore employed. In a continuous mode of operation, the conversion is preferably effected in a tank cascade. All cascade stages can work under reduced pressure; preferably, the pressure is reduced in the last stage of the cascade.
Preference is given to working under a vacuum between 900 and 0 bar.
According to the invention, the decrease in the residence time can also lead to a reduction in the content of compounds of formula (IV) in the end product.
Residence times between 0.1 and 11 h, preferably between 1 and 5 h, lead to a noticeable reduction in the content of compounds of formula (IV) in the end product.
For a sufficiently high conversion in spite of a reduced residence time, it is necessary that more active catalysts be used or/and that the amount of catalyst be increased.
9 To increase the reaction rate, the alcohol released in the reaction is drawn off from the reaction mixture by means of a distillation column, optionally also as an azeotrope with the alcohol. This can be effected either at atmospheric pressure or under reduced pressure.
The reaction mixture, consisting for the most part of the N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate product, unconverted (meth)acrylate and reactant, and small amounts of alcohol, the catalyst, the polymerization inhibitors and a proportion of by-products, after a reactor residence time of about 0.5-4 hours, preference being given to a residence time of 1-2 hours, is fed to a continuously operated falling-film evaporator. The vapours from the falling-film evaporator are fed to a low boiler distillation column. In this column, under reduced pressure, preferably in the range of about 1 mbar-500 mbar, the components that are low-boiling in relation to the product, predominantly product alcohol and unconverted reactant (meth)acrylate and reactant amine or alcohol, are removed. These are drawn off via the top of the distillation column and recycled into the reactor region or into the distillation column. This circulation stream achieves a high conversion based on the reactants and the overall process.
The crude product which is still contaminated with catalyst, polymerization inhibitor and high-boiling by-products and is obtained in the output from the falling-film evaporator contains preferably > 80%
by weight of product and, for workup, is fed to a further vacuum distillation stage which works within the preferred pressure range between 0.1 and 200 mbar. Here, the pure product is removed by distillation as the top product. Suitable apparatuses that are known for this purpose are falling-film, thin-film and short-path evaporators.
The preparation of the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates may optionally be followed downstream by a purifying distillation system which can also be operated under reduced pressure, for example at 500-0.1 mbar. This is necessary especially when a particularly good removal of the high-boiling secondary components formed in the process is to be effected.
The N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate prepared in accordance with the invention, having a low content of compounds of the formula (IV), can be reacted with an alkyl halide or alkyl sulphonate, preferably with methyl chloride, to give the corresponding quaternary ammonium salt.
N,N-(Di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof, having a low content of compounds of the formula (IV), are particularly suitable for the preparation of polymers which are brought into solution or else are polymerized in solution or as an emulsion or dispersion.
The reaction mixture, consisting for the most part of the N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate product, unconverted (meth)acrylate and reactant, and small amounts of alcohol, the catalyst, the polymerization inhibitors and a proportion of by-products, after a reactor residence time of about 0.5-4 hours, preference being given to a residence time of 1-2 hours, is fed to a continuously operated falling-film evaporator. The vapours from the falling-film evaporator are fed to a low boiler distillation column. In this column, under reduced pressure, preferably in the range of about 1 mbar-500 mbar, the components that are low-boiling in relation to the product, predominantly product alcohol and unconverted reactant (meth)acrylate and reactant amine or alcohol, are removed. These are drawn off via the top of the distillation column and recycled into the reactor region or into the distillation column. This circulation stream achieves a high conversion based on the reactants and the overall process.
The crude product which is still contaminated with catalyst, polymerization inhibitor and high-boiling by-products and is obtained in the output from the falling-film evaporator contains preferably > 80%
by weight of product and, for workup, is fed to a further vacuum distillation stage which works within the preferred pressure range between 0.1 and 200 mbar. Here, the pure product is removed by distillation as the top product. Suitable apparatuses that are known for this purpose are falling-film, thin-film and short-path evaporators.
The preparation of the N,N-(di)alkylaminoalkyl(meth)acrylamides or N,N-(di)alkylaminoalkyl (meth)acrylates may optionally be followed downstream by a purifying distillation system which can also be operated under reduced pressure, for example at 500-0.1 mbar. This is necessary especially when a particularly good removal of the high-boiling secondary components formed in the process is to be effected.
The N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate prepared in accordance with the invention, having a low content of compounds of the formula (IV), can be reacted with an alkyl halide or alkyl sulphonate, preferably with methyl chloride, to give the corresponding quaternary ammonium salt.
N,N-(Di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate and the quaternary ammonium salts thereof, having a low content of compounds of the formula (IV), are particularly suitable for the preparation of polymers which are brought into solution or else are polymerized in solution or as an emulsion or dispersion.
10 Preference is given to the use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 which are used for polymerization in the form of bulk polymerization, solution polymerization, dispersion polymerization or emulsion polymerization, and find use as thickeners, gelling agents, haircare compositions (conditioning polymers), fixatives, styling polymers, film formers, household/industrial and institutional cleaning, flocculants, water clarifiers, paper auxiliaries/additives, printing inks, flow improvers in the oil & gas industry and as gas hydrate inhibitors, etc.
Preference is likewise given to the use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 for conversion to quaternary ammonium salts which are used for polymerization and find use as thickeners, gelling agents, haircare compositions (conditioning polymers), fixatives, styling polymers, film formers, household/industrial and institutional cleaning, flocculants, water clarifiers, paper auxiliaries/additives, printing inks, flow improvers in the oil & gas industry and as gas hydrate inhibitors, etc.
The process according to the invention is elucidated in detail by the examples which follow, without being restricted thereto.
Examples Example 1 Synthesis of N,N-dimethylaminopropylmethacrylamide (DMAPMA) with exclusion of oxygen For continuous preparation of N,N-dimethylaminopropylmethacrylamide, the apparatus is operated under a nitrogen atmosphere. Into the 1st reaction tank are metered 200 kg/h of pre-activated catalyst feed having a content of 2.0% by weight of isopropyl titanate, 5.0%
by weight of dioctyltin oxide from the distillation column and 144 kg/h of N,N-dimethylaminopropylamine (DMAPA). The pre-activation was conducted in a stirred tank at 110 C for 2 h. In addition, the circulation return stream from the top of the low boiler distillation column flowed continuously to the 1st reaction tank via the distillation column (400 kg/h with the composition of 70% by weight of reactant methacrylate, and methanol, DMAPA and by-products). The molar MMA:DMAPA ratio in the reactor feed was 1.8:1. In addition, the vapours from the stirred tank which had been freed of methanol in the distillation column entered the 1st reaction tank via the bottom of the column.
Under these reaction conditions (pressure about 500 mbar), a reaction temperature of 105 C was established in the 1st reaction tank. The reaction temperatures in the 2nd and 3rd reaction tanks
Preference is likewise given to the use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 for conversion to quaternary ammonium salts which are used for polymerization and find use as thickeners, gelling agents, haircare compositions (conditioning polymers), fixatives, styling polymers, film formers, household/industrial and institutional cleaning, flocculants, water clarifiers, paper auxiliaries/additives, printing inks, flow improvers in the oil & gas industry and as gas hydrate inhibitors, etc.
The process according to the invention is elucidated in detail by the examples which follow, without being restricted thereto.
Examples Example 1 Synthesis of N,N-dimethylaminopropylmethacrylamide (DMAPMA) with exclusion of oxygen For continuous preparation of N,N-dimethylaminopropylmethacrylamide, the apparatus is operated under a nitrogen atmosphere. Into the 1st reaction tank are metered 200 kg/h of pre-activated catalyst feed having a content of 2.0% by weight of isopropyl titanate, 5.0%
by weight of dioctyltin oxide from the distillation column and 144 kg/h of N,N-dimethylaminopropylamine (DMAPA). The pre-activation was conducted in a stirred tank at 110 C for 2 h. In addition, the circulation return stream from the top of the low boiler distillation column flowed continuously to the 1st reaction tank via the distillation column (400 kg/h with the composition of 70% by weight of reactant methacrylate, and methanol, DMAPA and by-products). The molar MMA:DMAPA ratio in the reactor feed was 1.8:1. In addition, the vapours from the stirred tank which had been freed of methanol in the distillation column entered the 1st reaction tank via the bottom of the column.
Under these reaction conditions (pressure about 500 mbar), a reaction temperature of 105 C was established in the 1st reaction tank. The reaction temperatures in the 2nd and 3rd reaction tanks
11 were 115 C and 125 C respectively. The distillate draw rate from the distillation column was 110 kg/h.
The output from the 1st reaction tank ran into the 2nd reaction tank and the output from the 2nd reaction tank ran into the 3rd reaction tank. The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, methyl methacrylate (MMA) and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 230 kg/h and had the following composition: 98.5% by weight of DMAPMA, < 1% low boilers, about 0.5%
high boilers and 130 ppm of N-allylmethacrylamide.
Example 2 Synthesis of DMAPMA with exclusion of oxygen The crude ester is prepared according to Example 1.
The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, MMA and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 230 kg/h and had the following composition: 98.3% by weight of DMAPMA, < 1% low boilers, about 0.7% high boilers and 240 ppm of N-allylmethacrylamide.
Comparative Example 1 Synthesis of DMAPMA under oxygen For continuous preparation of N,N-dimethylaminopropylmethacrylamide, into the 1st reaction tank were metered 200 kg/h of pre-activated catalyst feed having a content of 2.0%
by weight of isopropyl titanate, 5.0% by weight of dioctyltin oxide from the distillation column and 144 kg/h of N,N-dimethylaminopropylamine (DMAPA). The pre-activation was conducted in a stirred tank at 110 C for 2 h. In addition, the circulation return stream from the top of the low boiler distillation column flowed continuously to the 1st reaction tank via the distillation column (400 kg/h with the composition of 70% by weight of reactant methacrylate, and methanol, DMAPA and by-products).
The output from the 1st reaction tank ran into the 2nd reaction tank and the output from the 2nd reaction tank ran into the 3rd reaction tank. The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, methyl methacrylate (MMA) and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 230 kg/h and had the following composition: 98.5% by weight of DMAPMA, < 1% low boilers, about 0.5%
high boilers and 130 ppm of N-allylmethacrylamide.
Example 2 Synthesis of DMAPMA with exclusion of oxygen The crude ester is prepared according to Example 1.
The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, MMA and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 230 kg/h and had the following composition: 98.3% by weight of DMAPMA, < 1% low boilers, about 0.7% high boilers and 240 ppm of N-allylmethacrylamide.
Comparative Example 1 Synthesis of DMAPMA under oxygen For continuous preparation of N,N-dimethylaminopropylmethacrylamide, into the 1st reaction tank were metered 200 kg/h of pre-activated catalyst feed having a content of 2.0%
by weight of isopropyl titanate, 5.0% by weight of dioctyltin oxide from the distillation column and 144 kg/h of N,N-dimethylaminopropylamine (DMAPA). The pre-activation was conducted in a stirred tank at 110 C for 2 h. In addition, the circulation return stream from the top of the low boiler distillation column flowed continuously to the 1st reaction tank via the distillation column (400 kg/h with the composition of 70% by weight of reactant methacrylate, and methanol, DMAPA and by-products).
12 The molar MMA:DMAPA ratio in the reactor feed was 1.8:1. In addition, the vapours from the stirred tank which had been freed of methanol in the distillation column entered the 1st reaction tank via the bottom of the column. Under these reaction conditions (pressure about 500 mbar), a reaction temperature of 138 C was established in the 1st reaction tank. The reaction temperatures in the 2nd and 3rd reaction tanks were 143 C and 155 C respectively. The distillate draw rate from the distillation column was 110 kg/h.
The output from the 1st reaction tank ran into the 2nd reaction tank and the output from the 2nd reaction tank ran into the 3rd reaction tank.
The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, MMA and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 240 kg/h and had the following composition: about 90% by weight of DMAPMA, 0.1% by weight of DMAPA, 0.16% by weight of N-allylmethacrylamide and a greater proportion of high-boiling components and traces of the reactants.
The crude product is subsequently worked up in a two-stage distillation.
Example 3 Laboratory study of the effect of oxygen on the formation of the compound of the formula (IV) DMAPMA was stabilized with a suitable amount of the stabilizers mentioned, and about 10 g of the stabilized DMAPMA in each case were introduced into test tubes. Each test tube contains an inlet tube for introduction of air or nitrogen. The samples were then heated in different oil baths to 110 C/120 C/130 C/140 C and 150 C, and air or nitrogen was introduced with a gas flow rate of about 0.75 l/h in each case over a period of 48 h. The samples were cooled and analysed by GC.
The N-allylmethacrylamide content in DMAPMA is shown in GC area% in the table below.
Temperature [ C] N-Allylmethacrylamide content in N-Allylmethacrylamide content in DMAPMA after 48 h / under air DMAPMA after 48 h / under [GC area%) nitrogen [GC area%]
110 1.69 0.34 120 7.87 0.33
The output from the 1st reaction tank ran into the 2nd reaction tank and the output from the 2nd reaction tank ran into the 3rd reaction tank.
The vapours from the individual reaction tanks were supplied continuously to a distillation column.
The output from the 3rd reaction tank continuously entered the thin-film evaporator of a low boiler column in which unconverted DMAPA, MMA and methanol were drawn off as distillate (400 kg/h) and fed back to the distillation column as circulation return stream. The bottoms output from the thin-film evaporator of the low boiler column was 240 kg/h and had the following composition: about 90% by weight of DMAPMA, 0.1% by weight of DMAPA, 0.16% by weight of N-allylmethacrylamide and a greater proportion of high-boiling components and traces of the reactants.
The crude product is subsequently worked up in a two-stage distillation.
Example 3 Laboratory study of the effect of oxygen on the formation of the compound of the formula (IV) DMAPMA was stabilized with a suitable amount of the stabilizers mentioned, and about 10 g of the stabilized DMAPMA in each case were introduced into test tubes. Each test tube contains an inlet tube for introduction of air or nitrogen. The samples were then heated in different oil baths to 110 C/120 C/130 C/140 C and 150 C, and air or nitrogen was introduced with a gas flow rate of about 0.75 l/h in each case over a period of 48 h. The samples were cooled and analysed by GC.
The N-allylmethacrylamide content in DMAPMA is shown in GC area% in the table below.
Temperature [ C] N-Allylmethacrylamide content in N-Allylmethacrylamide content in DMAPMA after 48 h / under air DMAPMA after 48 h / under [GC area%) nitrogen [GC area%]
110 1.69 0.34 120 7.87 0.33
13 130 11.08 0.32 140 21.97 0.32 150 23.54 0.33 Example 4 Determination of the limiting concentration Preparation of a copolymer from DMAPMA and N-allylmethacrylamide:
The DMAPMA (containing 130 ppm of N-allylmethacrylamide) was concentrated by the addition of N-allylmethacrylamide to a total concentration of N-allylmethacrylamide in the mixture of 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 1000 ppm, and 1200 ppm. (N-Allylmethacrylamide, from ABCR, Karlsruhe, Germany, batch: 1300868) Subsequently, 10 g in each case were initiated with 0.2% AIBN and polymerization was effected at 70 C in test tubes in a water bath within 3 h. The test tubes were cooled to room temperature overnight and then the glass was removed. A piece of polymer was taken from the solution.
Preparation of aqueous solutions:
The respective pieces of polymer were weighed into 125 ml wide-neck glass bottles and admixed with water to give a concentration of 3% or 5%. The solubility was checked for completeness after 96 h.
The viscosity of the homogeneous solutions was measured after 96 h by means of a Brookfield viscometer with a small-sample adapter (measurement apparatus for solutions having low viscosity).
Viscosity Viscosity N-Allylmethacrylamide content [3% in H20] [5% in H20]
130 ppm 24 mPa*s 35 mPa*s 300 ppm 28 mPa*s 37 mPa*s 400 ppm 31 mPa*s 45 mPa*s 500 ppm 33 mPa*s 51 mPa*s 600 ppm 33 mPa*s 60 mPa*s 700 ppm Not measurable* Not measurable*
800 ppm Not measurable* Not measurable*
"The viscosity is not measurable owing to the insolubility of the polymers.
The DMAPMA (containing 130 ppm of N-allylmethacrylamide) was concentrated by the addition of N-allylmethacrylamide to a total concentration of N-allylmethacrylamide in the mixture of 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 1000 ppm, and 1200 ppm. (N-Allylmethacrylamide, from ABCR, Karlsruhe, Germany, batch: 1300868) Subsequently, 10 g in each case were initiated with 0.2% AIBN and polymerization was effected at 70 C in test tubes in a water bath within 3 h. The test tubes were cooled to room temperature overnight and then the glass was removed. A piece of polymer was taken from the solution.
Preparation of aqueous solutions:
The respective pieces of polymer were weighed into 125 ml wide-neck glass bottles and admixed with water to give a concentration of 3% or 5%. The solubility was checked for completeness after 96 h.
The viscosity of the homogeneous solutions was measured after 96 h by means of a Brookfield viscometer with a small-sample adapter (measurement apparatus for solutions having low viscosity).
Viscosity Viscosity N-Allylmethacrylamide content [3% in H20] [5% in H20]
130 ppm 24 mPa*s 35 mPa*s 300 ppm 28 mPa*s 37 mPa*s 400 ppm 31 mPa*s 45 mPa*s 500 ppm 33 mPa*s 51 mPa*s 600 ppm 33 mPa*s 60 mPa*s 700 ppm Not measurable* Not measurable*
800 ppm Not measurable* Not measurable*
"The viscosity is not measurable owing to the insolubility of the polymers.
Claims (13)
1. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate of the general formula (I) <MG>
where R0 is hydrogen or methyl X is NH or O
R2, R3, R4 are each a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, having a content of less than 1200 ppm of the compound (IV) of the general formula where R5 in each case is a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, characterized in that the oxygen concentration is < 1000 ppm in the liquid phase in at least one component step of the preparation.
where R0 is hydrogen or methyl X is NH or O
R2, R3, R4 are each a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, having a content of less than 1200 ppm of the compound (IV) of the general formula where R5 in each case is a linear, branched or cyclic alkyl radical, an aryl radical which may also be substituted by one or more alkyl groups, the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, characterized in that the oxygen concentration is < 1000 ppm in the liquid phase in at least one component step of the preparation.
2. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1 having a content of less than 1200 ppm of the compound of the formula (IV) or quaternary ammonium salts thereof which are used for preparation of soluble or non-coagulating polymers.
3. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 2 having a content of less than 1000 ppm.
4. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that operation is effected with exclusion of oxygen.
5. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that the reaction is conducted under a protective gas atmosphere.
6. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that the residence time is 0.1-11 h, preferably 1-5 h.
7. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that the reaction is conducted at temperatures between 70°C and 160°C.
8. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 6, characterized in that the reaction is conducted under reduced pressure, preferably under vacuum.
9. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that the alcohol is removed during the reaction.
10. Process for preparing N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate according to Claim 1, characterized in that inhibitors from the group of bis(2-methoxycarbonylpropyl) sulphide, N,N-diethylhydroxylamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl or N,N'-diphenyl-p-phenylenediamine or derivatives thereof are used.
11. Use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 for reaction with alkyl halides or alkyl sulphonates to give quaternary ammonium salts which are used for polymerization.
12. Use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 which are used for polymerization in the form of bulk polymerization, solution polymerization, dispersion polymerization or emulsion polymerization, and find use as thickeners, gelling agents, haircare compositions, fixatives, styling polymers, film formers, household/industrial and institutional cleaning, flocculants, water clarifiers, paper auxiliaries/additives, printing inks, flow improvers in the oil & gas industry and as gas hydrate inhibitors.
13. Use of N,N-(di)alkylaminoalkyl(meth)acrylamide or N,N-(di)alkylaminoalkyl (meth)acrylate having a content of the compound of the formula (IV) of less than 1200 ppm prepared according to Claim 1 for conversion to quaternary ammonium salts which are used for polymerization, and find use as thickeners, gelling agents, haircare compositions, fixatives, styling polymers, film formers, household/industrial and institutional cleaning, flocculants, water clarifiers, paper auxiliaries/additives, printing inks, flow improvers in the oil & gas industry and as gas hydrate inhibitors.
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| AU2019272745A1 (en) | 2018-05-23 | 2021-01-21 | Evonik Operations Gmbh | Method for preparing keto-functionalized aromatic (meth)acrylates |
| SG11202100238TA (en) | 2018-07-17 | 2021-02-25 | Evonik Operations Gmbh | Method for preparing c-h acidic (meth)acrylates |
| EP3599232A1 (en) | 2018-07-26 | 2020-01-29 | Evonik Operations GmbH | Method for the preparation of n-methyl(meth)acrylamide |
| CN113493390A (en) * | 2020-04-01 | 2021-10-12 | 爱森（中国）絮凝剂有限公司 | Novel dialkyltin oxide composition and process for producing 2-dimethylaminoethyl (meth) acrylate |
| CN113861351B (en) * | 2020-06-30 | 2024-07-02 | 中国石油化工股份有限公司 | High-salt-resistant polyacrylamide copolymer, and preparation method and application thereof |
| CN115873171B (en) | 2021-09-29 | 2024-07-02 | 爱森（中国）絮凝剂有限公司 | 2-Dimethylaminoethyl acrylate polymer and preparation method thereof |
| US11767381B2 (en) | 2021-09-29 | 2023-09-26 | Snf Group | 2-dimethylaminoethyl acrylate polymers and their preparation method |
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| DE3235398C2 (en) | 1982-09-24 | 1986-04-24 | Chemische Fabrik Stockhausen GmbH, 4150 Krefeld | Process for the preparation of N-substituted acrylic acid amides |
| US4492801A (en) * | 1983-02-28 | 1985-01-08 | Texaco Inc. | Production of N-substituted (meth)acrylamides from (meth)acrylates and amines over a metal alkoxide catalyst |
| FR2590567B1 (en) * | 1985-11-27 | 1988-07-15 | Charbonnages Ste Chimique | NOVEL PROCESS FOR THE SYNTHESIS OF N-DIALKYLAMINOALKYL (METH) ACRYLAMIDE |
| JPS63234007A (en) | 1987-03-23 | 1988-09-29 | Kohjin Co Ltd | Highly water-soluble cationic polymer |
| JP2813602B2 (en) | 1989-01-31 | 1998-10-22 | 株式会社興人 | N, N-dialkylaminoalkyl (meth) acrylamide composition having improved storage stability |
| JPH0713050B2 (en) * | 1989-09-26 | 1995-02-15 | 東亞合成株式会社 | Method for producing dimethylaminoethyl acrylate |
| US5962578A (en) * | 1997-11-19 | 1999-10-05 | Amcol International Corporation | Poly(dialkylaminoalkyl (meth)acrylamide)-based superabsorbent gels |
| FR2777561B1 (en) * | 1998-04-21 | 2000-06-02 | Atochem Elf Sa | PROCESS FOR THE CONTINUOUS MANUFACTURE OF DIALKYLAMINOALKYL (METH) ACRYLATES |
| JP2000016966A (en) | 1998-07-01 | 2000-01-18 | Mitsubishi Gas Chem Co Inc | Production of hydroxyalkylacrylic ester or methacrylic acid ester |
| JP2000229919A (en) | 1999-02-12 | 2000-08-22 | Mitsubishi Rayon Co Ltd | Production of aqueous solution of high-purity unsaturated quaternary ammonium salt |
| WO2003101935A1 (en) * | 2002-06-04 | 2003-12-11 | Rhodia Inc. | Monomer compound comprising several cationic groups, process for making the same, and polymers comprising units deriving therefrom |
| CN1890358A (en) * | 2003-12-08 | 2007-01-03 | 罗迪亚公司 | Hydrophobic modified diquaternary monomers and polymers as thickening agents of acidic aqueous compositions |
| US7064232B2 (en) * | 2003-12-08 | 2006-06-20 | Rhodia Inc. | Hydrophobic modified diquaternary monomers and polymers as thickening agents of acidic aqueous compositions |
| CN101687768B (en) * | 2007-03-23 | 2014-05-28 | 罗迪亚公司 | Process for making a (meth) acrylamide monomer |
| DE102009002239A1 (en) | 2009-04-07 | 2010-10-14 | Evonik Röhm Gmbh | Process for the continuous production of alkylamino (meth) acrylamides |
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| CN107540565A (en) | 2018-01-05 |
| EP3263551A2 (en) | 2018-01-03 |
| MY173180A (en) | 2020-01-02 |
| MX2017008383A (en) | 2018-09-10 |
| TW201815745A (en) | 2018-05-01 |
| EP3263551A3 (en) | 2018-02-14 |
| KR20180002054A (en) | 2018-01-05 |
| JP2018002720A (en) | 2018-01-11 |
| RU2017122606A3 (en) | 2021-02-09 |
| TWI749022B (en) | 2021-12-11 |
| RU2757390C2 (en) | 2021-10-14 |
| JP7038495B2 (en) | 2022-03-18 |
| KR102463943B1 (en) | 2022-11-04 |
| SG10201705219QA (en) | 2018-01-30 |
| CN107540565B (en) | 2022-10-21 |
| EP3263551B1 (en) | 2020-10-14 |
| SG10201806830RA (en) | 2018-09-27 |
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